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| United States Patent |
5,691,412
|
|
Matsumura
, et al.
|
November 25, 1997
|
Polyamide/aliphatic polyester block copolymer, process for the
production thereof, and blend containing the same
Abstract
A polyamide/aliphatic polyester block copolymer (A) comprising a polyamide
block and an aliphatic polyester block, (B) satisfying the expression,
T.sub.1 -T<100-C (in which T is the melting point (.degree.C.) of the
above block copolymer, T.sub.1 is the melting point (.degree.C.) of a
polyamide composed of the polyamide block and C is the content (wt. %) of
the polyamide block), (C) exhibiting the extraction amount which satisfies
the expression, when extracted in tetrahydrofuran, E<(100-C).times.0.4 (in
which E is the extraction amount (wt. %) when the block copolymer is
refluxed in tetrahydrofuran, and C is the content (wt. %) of the polyamide
block) and (D) having an intrinsic viscosity, measured at 35.degree. C.,
in the range of from 0.5 to 5; a process for the production thereof; a
fiber formed therefrom; and an intimate blend comprising a thermoplastic
resin having no or poor compatibility with polyamide and the block
copolymer.
| Inventors:
|
Matsumura; Shunichi (Iwakuni, JP);
Ito; Takashi (Iwakuni, JP);
Miyoshi; Takanori (Iwakuni, JP)
|
| Assignee:
|
Teijin Limited (Osaka, JP)
|
| Appl. No.:
|
449939 |
| Filed:
|
May 25, 1995 |
Foreign Application Priority Data
| Feb 23, 1993[JP] | 5-33189 |
| Apr 20, 1993[JP] | 5-93028 |
| Jul 14, 1993[JP] | 5-174279 |
| Aug 26, 1993[JP] | 5-211368 |
| Nov 01, 1993[JP] | 5-273482 |
| Current U.S. Class: |
525/66; 525/92A; 525/394; 525/397; 525/420; 525/425; 525/432 |
| Intern'l Class: |
C08L 077/00 |
| Field of Search: |
525/425,420,66,92 A,394,397,432
|
References Cited
U.S. Patent Documents
| 3554983 | Jan., 1971 | Goodman et al.
| |
| 3758631 | Sep., 1973 | Werner et al.
| |
| 4588785 | May., 1986 | Bax et al. | 525/419.
|
| 5093437 | Mar., 1992 | Komiya et al. | 525/440.
|
| Foreign Patent Documents |
| 2233853 | Jun., 1973 | FR.
| |
| 54-119594 | Sep., 1979 | JP.
| |
| 1140463 | Jan., 1969 | GB.
| |
Primary Examiner: Woodward; Ana
Attorney, Agent or Firm: Sherman and Shalloway
Parent Case Text
This is a division of application Ser. No, 08/200,454 filed Feb. 23, 1994,
which issued as U.S. Pat. No. 5,446,109 on Aug. 29, 1995.
Claims
What is claimed is:
1. An intimate blend comprising a thermoplastic resin having no or poor
compatibility with polyamide, a polyamide resin and a compatibilizing
agent, said thermoplastic resin being selected from the group consisting
of a polyester resin, a polycarbonate resin, a polyester carbonate resin,
an acrylonitrile-butadiene-styrene resin, an acrylonitrile-styrene resin
and a polyphenylene oxide resin, and said compatibilizing agent being a
polyamide/aliphatic polyester block copolymer comprising
(A) (I) a polyamide block composed substantially of at least one recurring
unit selected from the group consisting of a recurring unit of the formula
(1),
##STR19##
wherein R.sub.1 is an alkylene group having 4 to 12 carbon atoms, a
recurring unit of the formula (2)
##STR20##
wherein R.sub.2 is an alkylene group having 4 to 12 carbon atoms or an
alkylene-arylene-alkylene group having 8 to 16 carbon atoms, and R.sub.3
is an alkylene group having 4 to 12 carbon atoms or an arylene group
having 6 to 12 carbon atoms, and mixtures of recurring units of formula
(1) and formula (2);
and (II) an aliphatic polyester block composed substantially of at least
one recurring unit selected from the group consisting of a recurring unit
of the formula (3)
##STR21##
wherein R.sub.4 is an alkylene group having 1 to 12 carbon atoms, a
recurring unit of the formula (4)
##STR22##
wherein R.sub.5 is an alkylene group having 2 to 12 carbon atoms and
R.sub.6 is an alkylene group having 2 to 12 carbon atoms, and mixtures of
recurring units of formula (3) and formula (4);
said block copolymer having the following properties (B), (C) and (D):
(B) satisfying the following expression (5),
T.sub.1 -T<100-C (5)
wherein T is the melting point (.degree.C.) of the above block copolymer,
T.sub.1 is the melting point (.degree.C.) of a polyamide composed of the
polyamide block and C is the content (wt. %) of the polyamide block,
(C) exhibiting the extraction amount which satisfies the expression (6),
when extracted in tetrahydrofuran,
E<(100-C).times.0.4 (6)
wherein E is the extraction amount (wt. %) when the block copolymer is
refluxed in tetrahydrofuran of which the weight is 100 times the weight of
the block copolymer under heat for 2 hours, and C is the content (wt. %)
of the polyamide block, and
(D) having an intrinsic viscosity, measured at 35.degree. C., in the range
of from 0.5 to 5.
2. The intimate blend of claim 1 which comprises from 1 to 50 parts by
weight of the compatibilizing agent per 100 parts by weight, in total, of
the thermoplastic resin and the polyamide.
3. The intimate blend of claim 2 wherein the weight ratio of the
thermoplastic resin to the polyamide is from 95/5 to 5/95.
4. The intimate blend of claim 4 wherein the amount of the compatibilizing
agent is from 2 to 40 parts per 100 parts, in total, of the thermoplastic
resin and polyamide.
5. The intimate blend of claim 1 which comprises from 3 to 30 parts by
weight of the compatibilizing agent and 100 parts by weight, in total, of
the thermoplastic resin and polyamide, and wherein the weight ratio of the
thermoplastic resin to polyamide is in the range of from 90/10 to 10/90.
6. The intimate blend according to claim 1 wherein the thermoplastic resin
is said polycarbonate resin.
7. The intimate blend according to claim 6 wherein the polycarbonate resin
has a viscosity-average molecular weight of from 15,000 to 40,000.
8. The intimate blend of claim 1 wherein the recurring units of polyamide
block (I) are nylon 6 or nylon 66 or mixture thereof and the recurring
units of aliphatic polyester block (II) are polycaprolactone, polyethylene
sebacate, polytetramethylene sebacate or polyneopentylene sebacate or
mixture thereof.
9. The intimate blend of claim 1 wherein the polyamide resin comprises
nylon 6.
10. The intimate blend of claim 9 wherein the block copolymer comprises as
recurring units (I) nylon 6 and as recurring units (II) polycaprolactone.
11. The intimate blend of claim 10 wherein the thermoplastic resin
comprises said polycarbonate resin.
12. The intimate blend of claim of claim 1 wherein the block copolymer
comprises as recurring units (I) nylon 6 and as recurring units (II)
polycaprolactone.
13. A method for forming an intimate blend of a thermoplastic resin having
no or poor compatibility with a polyamide, and a polyamide, which
comprises intimately blending a thermoplastic resin selected from the
group consisting of a polyester resin, a polycarbonate resin, a polyester
carbonate resin, an acrylonitrile-butadiene-styrene resin, an
acrylonitrile-styrene resin and a polyphenylene oxide resin, and the
polyamide in the presence of a compatibilizing agent comprising a
polyamide/aliphatic polyester block copolymer comprising
(A) a polyamide block composed substantially of at least one recurring unit
selected from the group consisting of a recurring unit of the formula (1),
##STR23##
wherein R.sub.1 is an alkylene group having 4 to 12 carbon atoms,
recurring unit of the formula (2)
##STR24##
wherein R.sub.2 is an alkylene group having 4 to 12 carbon atoms or an
alkylene-arylene-alkylene group having 8 to 16 carbon atoms, and R.sub.3
is an alkylene group having 4 to 12 carbon atoms or an arylene group
having 6 to 12 carbon atoms, and mixtures of recurring units of formula
(1) and formula (2);
and an aliphatic polyester block composed substantially of at least one
recurring unit selected from the group consisting of a recurring unit of
the formula (3)
##STR25##
wherein R.sub.4 is an alkylene group having 1 to 12 carbon atoms, a
recurring unit of the formula (4)
##STR26##
wherein R.sub.5 is an alkylene group having 2 to 12 carbon atoms and
R.sub.6 is an alkylene group having 2 to 12 carbon atoms, and mixtures of
recurring units of formula (3) and formula (4);
said block copolymer having the following properties (B), (C) and (D):
(B) satisfying the following expression (5),
T.sub.1 -T<100-C (5)
wherein T is the melting point (.degree.C.) of the above block copolymer,
T.sub.1 is the melting point (.degree.C.) of a polyamide composed of the
polyamide block and C is the content (wt. %) of the polyamide block,
(C) exhibiting the extraction amount which satisfies the expression (6),
when extracted in tetrahydrofuran,
E<(100-C).times.0.4 (6)
wherein E is the extraction amount (wt. %) when the block copolymer is
refluxed in tetrahydrofuran of which the weight is 100 times the weight of
the block copolymer under heat for 2 hours, and C is the content (wt. %)
of the polyamide block, and
(D) having an intrinsic viscosity, measured at 35.degree. C., in the range
of from 0.5 to 5.
14. The method of claim 13 wherein the step of intimately blending
comprises melt-kneading the thermoplastic resin, the polyamide and the
compatibilizing agent.
15. The method of claim 13 which comprises intimately blending from 1 to 50
parts by weight of the compatibilizing agent with 100 parts by weight, in
total, of the thermoplastic resin and the polyamide.
16. The method of claim 15 wherein the thermoplastic resin and the
polyamide are incorporated in the intimate blend at a weight ratio of from
95/5 to 5/95.
17. The method according to claim 13 wherein the thermoplastic resin is
said polycarbonate resin.
18. The method according to claim 17 wherein the polycarbonate resin has a
viscosity-average molecular weight of from 15,000 to 40,000.
19. An intimate blend comprising the product obtained by intimately
blending a thermoplastic resin having no or poor compatibility with
polyamide, a polyamide resin and a compatibilizing agent, said
thermoplastic resin being selected from the group consisting of a
polyester resin, a polycarbonate resin, a polyester carbonate resin, an
acrylonitrile-butadiene-styrene resin, an acrylonitrile-styrene resin and
a polyphenylene oxide resin, and said compatibilizing agent being a
polyamide/aliphatic polyester block copolymer comprising
(A) (I) a polyamide block composed substantially of at least one recurring
unit selected from the group consisting of a recurring unit of the formula
(1),
##STR27##
wherein R.sub.1 is an alkylene group having 4 to 12 carbon atoms,
recurring unit of the formula (2)
##STR28##
wherein R.sub.2 is an alkylene group having 4 to 12 carbon atoms or an
alkylene-arylene-alkylene group having 8 to 16 carbon atoms, and R.sub.3
is an alkylene group having 4 to 12 carbon atoms or an arylene group
having 6 to 12 carbon atoms, and mixtures of recurring units of formula
(1) and formula (2);
and (II) an aliphatic polyester block composed substantially of at least
one recurring unit selected from the group consisting of a recurring unit
of the formula (3)
##STR29##
wherein R.sub.4 is an alkylene group having 1 to 12 carbon atoms, a
recurring unit of the formula (4)
##STR30##
wherein R.sub.5 is an alkylene group having 2 to 12 carbon atoms and
R.sub.6 is an alkylene group having 2 to 12 carbon atoms and mixtures of
recurring units of formula (3) and formula (4);
said block copolymer having the following properties (B), (C) and (D):
(B) satisfying the following expression (5),
T.sub.1 -T<100-C (5)
wherein T is the melting point (.degree.C.) of the above block copolymer,
T.sub.1 is the melting point (.degree.C.) of a polyamide composed of the
polyamide block and C is the content (wt. %) of the polyamide block,
(C) exhibiting the extraction amount which satisfies the expression (6),
when extracted in tetrahydrofuran,
E<(100-C).times.0.4 (6)
wherein E is the extraction amount (wt. %) when the block copolymer is
refluxed in tetrahydrofuran of which the weight is 100 times the weight of
the block copolymer under heat for 2 hours, and C is the content (wt. %)
of the polyamide block, and
(D) having an intrinsic viscosity, measured at 35.degree. C., in the range
of from 0.5 to 5.
20. The intimate blend according to claim 19 wherein the block copolymer is
the product obtained by melt-reacting (A) said polyamide composed
substantially of the recurring units of formula (1) or recurring units of
formula (2) or recurring units of a mixture of formula (1) and formula (2)
and (B) said aliphatic polyester composed substantially of the recurring
units of formula (3) or recurring units of formula (4) or recurring units
of a mixture of formula (3) and formula (4), in the presence of an
aromatic monohydroxy compound in an amount of 5 to 100 parts by weight per
100 parts by weight of the total amount of (A) and (B) and in the presence
of an ester interchange catalyst, and distilling off the aromatic
monohydroxy compound.
21. The intimate blend of claim 20 wherein the recurring units of the block
copolymer are (I) nylon 6 or nylon 66 or mixture thereof and (II)
polycaprolactone, polyethylene sebacate, polytetramethylene sebacate or
polyneopentylene sebacate or mixture thereof.
22. The intimate blend of claim 20 wherein the recurring units of the block
copolymer are (I) nylon 6 and (II) polycaprolactone.
23. The intimate blend of claim 22 wherein the thermoplastic resin is said
polycarbonate resin.
24. The intimate blend of claim 23 wherein the polyamide resin is nylon 6.
25. The intimate blend of claim 19 wherein the thermoplastic resin is said
polycarbonate.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a polyamide/aliphatic polyester block
copolymer, a process for the production thereof and a blend containing the
same. More specifically, it relates to a polyamide/aliphatic polyester
block copolymer which exhibits excellent thermal stability and good
melt-fluidity, a process for the production thereof and a blend containing
the same.
Japanese Patent Publication No. 19265/1967 discloses a method in which a
polyamide having terminal amino groups is melt-reacted under heat with a
six- or seven-membered lactone such as .delta.-valerolactone or
.epsilon.-caprolactone. The block copolymer obtained by this method has a
softening point which shows that the degree of randomness is considerably
high.
Japanese Patent Publication No. 29468/1969 discloses a method in which
caprolactam and caprolactone are allowed to react in the presence of metal
sodium to produce a polyester-polyamide copolymer. The polyester-polyamide
copolymer obtained by this method shows the linearity in the relationship
between the polymer composition and melting point as is described in the
said Publication. Therefore, it is different from a typical random
copolymer which shows a downward convex form in the above relationship,
but it is a block copolymer whose randomness degree is considerably high.
Similarly to Japanese Patent Publication No. 29468/1969, Eur. Polym. J.
Vol. 20, No. 6, pages 529-537 (1984) discloses a method in which
.epsilon.-caprolactone and .epsilon.-caprolactam are polymerized in a
ring-opening polymerization to produce a copolymer of polycaprolactone and
polycaprolactam.
Japanese Patent Publication No. 26688/1982 discloses a method for producing
a biodegradable polyester amide copolymer, in which a mixture of a
polycaprolactone having a high molecular weight and an aliphatic polyamide
having a high molecular weight is melted by heating it to a temperature
equal to, or higher than, the melting points of these and the ester/amide
exchange reaction is carried out until a product which shows a clear drop
in melting point is obtained. The melting point of the copolymer disclosed
in the said Publication shows that the said copolymer has a considerably
high degree of randomness.
Japanese Laid-open Patent Publication No. 171731/1986 discloses a
polycaprolactoneamide elastomer which contains 20 to 90% by weight of a
polyamide component and 80 to 10% by weight of a polycaprolactone
component and is excellent in impact absorption.
Japanese Laid-open Patent Publication No. 306229/1992 discloses a
biodegradable polyesteramide copolymer which contains an aliphatic
polyester block and an aromatic polyamide block and has a melting point
lower than that of the aromatic polyamide used as a raw material. As a
method for producing this biodegradable polyesteramide copolymer, the said
Publication discloses a method in which a mixture of a polyester and a
polyamide is allowed to react by heating it to a temperature equal to, or
higher than, the melting or softening points of these in an inert gas
until the formation of a product which shows a clear drop in melting point
from the melting or softening points of these.
In the method of reacting polyester and polyamide in an ester/amide
exchange reaction while they are melted, it is required to react them at a
high temperature for a long period of time, and the productivity is hence
very low, since polyamide and polyester are inherently incompatible with
each other. Further, this method is also very disadvantageous in terms of
energy since a copolymer is formed by sectioning the chain of a polymer
once produced as one having a high polymerization degree.
Japanese Laid-open Patent Publication No. 156010/1993 discloses a method
for producing a biodegradable polylactoneamide resin containing 5 to 70%
by weight of polyamide units and 30 to 95% by weight of polylactone units,
in which a polyamide-forming compound and a polylactone compound having an
average molecular weight of at least 10,000 are allowed to react.
It is an object of the present invention to provide a novel
polyamide/aliphatic polyester block copolymer.
It is another object of the present invention to provide a
polyamide/aliphatic polyester block copolymer whose randomness degree is
highly inhibited and which therefore exhibits a remarkably high melting
point over that of a random copolymer.
It is further another object of the present invention to provide a
polyamide/aliphatic polyester block copolymer which has a high degree of
block segment formation and whose polyamide and aliphatic polyester
contents are inhibited to remarkably low degrees.
It is still further another object of the present invention to provide a
process for producing the above polyamide/aliphatic polyester block
copolymer of the present invention industrially advantageously.
It is yet another object of the present invention to provide a
polyamide/aliphatic polyester block copolymer having the shape memory and
restoration capability.
It is yet another object of the present invention to provide a resin blend
containing the above polyamide/aliphatic polyester block copolymer of the
present invention, e.g., a resin blend containing the above
polyamide/aliphatic polyester block copolymer of the present invention as
a compatibilizing agent for intimately mixing resins which are poor in
compatibility to each other.
Other objects and advantages of the present invention will be apparent from
the following description.
The above objects and advantages of the present invention are achieved,
first, by a polyamide/aliphatic polyester block copolymer;
(A) comprising a polyamide block composed substantially of at least one of
a recurring unit of the formula (1),
##STR1##
wherein R.sub.1 is an alkylene group having 4 to 12 carbon atoms, and a
recurring unit of the formula (2),
##STR2##
wherein R.sub.2 is an alkylene group having 4 to 12 carbon atoms or an
alkylene-arylene-alkylene group having 8 to 16 carbon atoms, and R.sub.3
is an alkylene group having 4 to 12 carbon atoms or an arylene group
having 6 to 12 carbon atoms, and an aliphatic polyester block composed
substantially of at least one of a recurring unit of the formula (3),
##STR3##
wherein R.sub.4 is an alkylene group having 1 to 12 carbon atoms, and a
recurring unit of the formula (4),
##STR4##
wherein R.sub.5 is an alkylene group having 2 to 12 carbon atoms and
R.sub.6 is an alkylene group having 2 to 12 carbon atoms or a combination
of an alkylene group having 2 to 12 carbon atoms and a divalent aromatic
group,
(B) satisfying the following expression (5), T.sub.1 -T<100-C . . . (5)
wherein T is the melting point (.degree.C.) of the above block copolymer,
T.sub.1 is the melting point (.degree.C.) of a polyamide composed of the
polyamide block and C is the content (wt. %) of the polyamide block,
(C) exhibiting the extraction amount which satisfies the expression (6),
when extracted in tetrahydrofuran,
E<(100-C).times.0.4 . . . (6) wherein E is the extraction amount (wt. %)
when the block copolymer is refluxed in tetrahydrofuran of which the
weight is 100 times the weight of the block copolymer under heat for 2
hours, and C is the content (wt. %) of the polyamide block, and
(D) having an intrinsic viscosity, measured at 35.degree. C., in the range
of from 0.5 to 5.
FIG. 1 is the scanning electron microscopic photograph of a block copolymer
(Example 1) of the present invention.
FIG. 2 is a scanning electron microscopic photograph of a conventional
block copolymer (Comparative Example 1).
FIG. 3 shows the shape memory capability of a shape memory fiber (Example
21) obtained from a block copolymer of the present invention.
FIG. 4 is the shape memory capability of a shape memory fiber (Example 22)
obtained from another block copolymer of the present invention.
The polyamide/aliphatic polyester block copolymer of the present invention
is defined by the above requirements (A), (B), (C) and (D).
The requirement (A) defines that the above block copolymer of the present
invention comprises a polyamide block composed essentially of at least one
of the recurring unit of the formula (1) and the recurring unit of the
formula (2) and an aliphatic polyester block composed substantially of at
least one of the recurring unit of the formula (3) and the recurring unit
of the formula (4).
In the formula (1), R.sub.1 is an alkylene group having 4 to 12 carbon
atoms. This alkylene group may be linear or branched, while a linear
alkylene group is preferred. Examples of this alkylene group include
tetramethylene, pentamethylene, hexamethylene, decamethylene,
undecamethylene and dodecamethylene. Of these, pentamethylene is
preferred. When R.sub.1 is pentamethylene, the above formula (1) is
represented by the following formula (1)-a.
##STR5##
Examples of the recurring unit of the above formula (1) further include
##STR6##
In the formula (2), R.sub.2 is an alkylene group having 4 to 12 carbon
atoms or an alkylene-arylene-alkylene group having 8 to 16 carbon atoms,
and R.sub.3 is an alkylene group having 4 to 12 carbon atoms or an arylene
group having 6 to 12 carbon atoms.
The alkylene group having 4 to 12 as each of R.sub.2 and R.sub.3 may be
linear, branched or cyclic.
Examples of each alkylene group above include tetramethylene,
hexamethylene, octamethylene, decamethylene, dodecamethylene,
neopentylene, 2,2,4-trimethylhexamethylene, 2,4,4-trimethylhexamethylene
and 1,4-cyclohexylene.
Examples of the alkylene-arylene-alkylene group having 8 to 16 carbon atoms
as R.sub.2 include p-xylylene, m-xylylene,
##STR7##
Further, examples of the arylene group having 6 to 12 carbon atoms as
R.sub.3 include m-phenylene, p-phenylene, 2,6-naphthylene and
1,4-biphenylene.
Of these, hexamethylene is preferred as R.sub.2, and tetramethylene is
preferred as R.sub.3. In this case, the above formula (2) is represented
by the following formula (2)-a.
##STR8##
Examples of the recurring unit of the above formula (2) further include
##STR9##
In the present invention, the polyamide block is composed substantially of
the recurring unit of the above formula (1) or is composed substantially
of the recurring unit of the above formula (2) or is composed of the
recurring unit of the above formula (1) and the recurring unit of the
above formula (2).
In the aliphatic polyester block, R.sub.4 in the formula (3) is an alkylene
group having 1 to 12 carbon atoms. This alkylene group may be linear or
branched, while a linear alkylene group is preferred.
Examples of the above alkylene group include methylene, methylmethylene,
tetramethylene, ethylene, trimethylene, tetramethylene, pentamethylene,
hexamethylene, decamethylene and undecamethylene. Of these, methylene,
methylmethylene and pentamethylene are preferred. Pentamethylene is
particularly preferred. In this case, the above formula (3) represents a
caprolactone block of the following formula (3)-a.
##STR10##
In the formula (4), R.sub.5 is an alkylene group having 2 to 12 carbon
atoms.
This alkylene group may be linear, branched or cyclic.
Examples of the above alkylene group include ethylene, trimethylene,
tetramethylene, hexamethylene, octamethylene, decamethylene,
dodecamethylene, neopentylene, 3-methylpentamethylene,
2,2,4-trimethylhexamethylene, 2,4,4-trimethylhexamethylene and
1,4-cyclohexylene.
In the formula (4), further, R.sub.6 is an alkylene group having 2 to 12
carbon atoms or a combination of an alkylene group having 2 to 12 carbon
atoms with a divalent aromatic group.
Examples of each of the above alkylene groups having 2 to 12 carbon atoms
include those described concerning R.sub.5 above.
In the combination of an alkylene group having 2 to 12 carbon atoms with a
divalent aromatic group, the divalent aromatic group is preferably a
subordinate component, and the content of the component unit from the
divalent aromatic group on the basis of the total of the recurring units
is preferably 30 mol % or less, more preferably 20 mol % or less,
particularly preferably 10 mol % or less. Examples of the divalent
aromatic group include
##STR11##
in which M is an alkali metal atom, a quaternary ammonium group or a
quaternary phosphonium group.
The block copolymer of the present invention, containing a small amount of
the component from
##STR12##
shows a low surface resistivity, has permanent antistatic properties and
hence can be used as a permanent antistatic agent for other thermoplastic
resins.
In the present invention, the aliphatic polyester block is composed
substantially of the recurring unit of the above formula (3) or is
composed substantially of the recurring unit of the above formula (4) or
is composed substantially of the recurring unit of the above formula (3)
and the recurring unit of the above formula (4).
In the block copolymer of the present invention, the content of the
polyamide block is 5 to 90% by weight, and the content of the aliphatic
polyester block is 95 to 10% by weight. Preferably, the content of the
polyamide block is 7 to 85% by weight, and the content of the aliphatic
polyester block is 93 to 15% by weight. Particularly preferably, the
content of the polyamide block is 10 to 80% by weight, and the content of
the aliphatic polyester block is 90 to 20% by weight.
The requirement (B) defining the block copolymer of the present invention
shows that the randomness degree of the block copolymer of the present
invention is highly inhibited.
That is, the requirement (B) defines that the block copolymer of the
present invention satisfies the following expression (5).
T.sub.1 -T<100-C (5)
wherein T is the melting point (.degree.C.) of the block copolymer, T.sub.1
is the melting point of a polyamide composed of the polyamide block and C
is the content (wt. %) of the polyamide block.
T.sub.1 is a melting point of a polyamide comprising the polyamide block
composed of at least one of a recurring unit of the formula (1) and a
recurring unit of the formula (2).
Under the conditions satisfying the formula (5), preferably, the block
copolymer of the present invention satisfies the following expression
(5)-a.
T.sub.1 -T<0.8(100-C) (5)-a
wherein T.sub.1, T and C are as defined in the expression (5).
The requirement (C) defining the block copolymer of the present invention
shows that the block copolymer has a high degree of block segment
formation and that the aliphatic polyester content is inhibited to
remarkably low degrees.
That is, the requirement (C) defines that the block copolymer of the
present invention exhibits the extraction amount which satisfies the
expression (6), when extracted in tetrahydrofuran,
E<(100-C).times.0.4 (6)
wherein E is the extraction amount (wt. %) when the block copolymer is
refluxed in tetrahydrofuran of which the weight is 100 times the weight of
the block copolymer under heat for 2 hours, and C is the content (wt. %)
of the polyamide block.
The above expression for example shows that when the polyamide block
content is 50% by weight, the extraction amount in tetrahydrofuran is less
than 20% by weight. An aliphatic polyester other than the block copolymer
is not all that are included in the extract resulting from the extraction
in tetrahydrofuran, while the extract at least includes an aliphatic
polyester which does not constitute the block segment.
The block copolymer of the present invention preferably exhibits the
extraction amount which satisfies the following expression,
E<(100-C).times.0.3 (6)-a
wherein E and C are as defined in the expression (5).
The final requirement (D) defining the block copolymer of the present
invention is that the block copolymer of the present invention has an
intrinsic viscosity, measured in a phenol/1,1,2,2-tetrachloroethane mixed
solvent (weight ratio 60/40) at 35.degree. C., in the range of from 0.5 to
5. This intrinsic viscosity at 35.degree. C. is preferably in the range of
from 0.6 to 3.
The block copolymer of the present invention is used in a variety of fields
as will be explained later. The block copolymer of the present invention
also has its characteristic feature in that it is biodegradable.
According to the present invention, as a process for the production of a
polyamide/aliphatic polyester block copolymer including the above block
copolymer of the present invention, there is also provided a process
comprising melt-reacting under heat
(A) a polyamide composed substantially of at least one of a recurring unit
of the formula (1),
##STR13##
wherein R.sub.1 is an alkylene group having 4 to 12 carbon atoms, and a
recurring unit of the formula (2),
##STR14##
wherein R.sub.2 is an alkylene group having 4 to 12 carbon atoms or an
alkylene-arylene-alkylene group having 8 to 16 carbon atoms, and R.sub.3
is an alkylene group having 4 to 12 carbon atoms or an arylene group
having 6 to 12 carbon atoms, and
(B) at least one of an aliphatic polyester and .epsilon.-caprolactone
(C) in the presence of an aromatic monohydroxy compound in an amount of 5
to 100 parts by weight per 100 parts by weight of the total amount of the
above components (A) and (B) and in the presence of an ester interchange
catalyst, and then distilling off the above aromatic monohydroxy compound.
In the process of the present invention, the polyamide (A) and at least one
component (B) of an aliphatic polyester and .epsilon.-caprolactone are
allowed to react in the presence of an aromatic hydroxy compound and an
ester interchange catalyst by melting these components under heat.
The polyamide used as a raw material is composed substantially of at least
one of the recurring unit of the above formula (1) and the recurring unit
of the above formula (2).
The above formulae (1) and (2) are already explained.
Examples of the above polyamide include nylon 6, nylon 66, nylon 610, nylon
612, nylon 11, nylon 12, 35 nylon MXD6, nylon 46,
polyhexamethyleneisophthalamide, polytrimethylhexamethyleneterephthalamide
and a copolyamide obtained by copolymerizing at least two of these
polyamides. Of these, nylon 6 and nylon 66 are preferred as the polyamide.
These polyamides may be used alone or in combination. These polyamides
prepared, for example, for producing a fiber, a film or a plastic may be
used as they are. The molecular weight of the polyamide is not specially
limited, while it is preferred to use, for example, a polyamide having an
intrinsic viscosity, measured in m-cresol at 35.degree. C., of
approximately 0.3 to 3.0.
As the aliphatic polyester used as the other raw material, preferred is,
for example, an aliphatic polyester composed substantially of at least one
of the recurring unit of the above formula (3) and the recurring unit of
the above formula (4).
Examples of the above aliphatic polyester include polycaprolactone,
polypropiolactone, polyvalerolactone, polylactate, polyglycolate,
polyethylene adipate, polyethylene succinate, polyethylene azelate,
polyethylene sebacate, polytrimethylene sebacate, polytetramethylene
sebacate, polyhexamethylene sebacate, polyoctamethylene sebacate,
polydecamethylene sebacate, polyneopentylene sebacate and a copolyester
obtained by copolymerizing at least two of these aliphatic polyesters. Of
these, preferred are polycaprolactone, polyethylene sebacate,
polytetramethylene sebacate and polyneopentylene sebacate. These
polyesters may be used alone or in combination.
The molecular weight of the aliphatic polyester is not specially limited,
while it is advantageous to use, for example, an aliphatic polyester
having an intrinsic viscosity, measured in a
phenol/1,1,2,2-tetrachloroethane mixed solvent (weight ratio 60/40) at
35.degree. C., of approximately 0.03 to 3.0, preferably approximately 0.5
to 2.5.
In the process of the present invention, .epsilon.-caprolactone may be used
in place of, or together with, the above aliphatic polyester.
In the process of the present invention, the weight ratio of the above
polyamide/the aliphatic polyester and/or .epsilon.-caprolactone is
preferably 5/95 to 90/10. When the proportion of the polyamide is less
than 5, the resultant copolymer is poor in heat resistance. When it is
greater than 90, the resultant copolymer is poor in properties exhibited
by the copolymerization of the aliphatic polyester, such as
biodegradability. The weight ratio of the polyamide/the aliphatic
polyester and/or .epsilon.-caprolactone is preferably 7/93 to 85/15,
particularly preferably 10/90 to 80/20.
In addition, .epsilon.-caprolactone undergoes ring-opening polymerization
during the reaction during the melt-reaction.
The aromatic monohydroxy compound used in the reaction has the function as
a compatibilizing agent between the polyamide and the aliphatic polyester,
and as a result, causes a reaction of a terminal amino group and/or a
carboxyl group of the polyamide, and the aliphatic polyester or an
amide/ester interchange reaction of the polyamide and the polyester,
whereby the intended block copolymer can be effectively obtained.
As the aromatic monohydroxy compound, preferred is a compound of the
formula (7),
##STR15##
wherein X is an alkyl group having 1 to 3 carbon atoms or a halogen atom,
and m is an integer of 0 to 3.
Examples of the above monohydroxy compound includes phenol, m-cresol,
p-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol,
2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, m-ethylphenol,
o-ethylphenol, p-ethylphenol, p-propylphenol, o-propylphenol,
m-propylphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol,
2,4-dichlorophenol, 2,3-dichlorophenol, 2,5-dichlorophenol, and
2,4,6-trichlorophenol.
The amount of the aromatic monohydroxy compound per 100 parts by weight of
the total amount of the polyamide and the aliphatic polyester and/or
.epsilon.-caprolactone is 5 to 100 parts by weight. When the above amount
of the aromatic monohydroxy compound is less than 5 parts by weight,
undesirably, the function of the aromatic monohydroxy compound as the
compatibilizing agent is insufficient. When the above amount is larger
than 100 parts by weight, undesirably, the step of distilling off the
aromatic monohydroxy compound after the polymerization takes a long period
of time. The amount of the aromatic monohydroxy compound per 100 parts by
weight of the total amount of the polyamide and the aliphatic polyester
and/or .epsilon.-caprolactone is preferably 10 to 50 parts by weight.
The temperature for the reaction under heat is not specially limited, and
it is sufficient to use a temperature at which the polyamide and the
aliphatic polyester are dissolved or melted in the polymerization system.
The temperature for the reaction is preferably 180.degree. to 320.degree.
C., more preferably 200.degree. to 300.degree. C.
For promoting the above reaction, a catalyst is added to the melt-reaction
system. The catalyst is selected from those known as an ester interchange
catalyst. Examples of the catalyst preferably include alkali metal
compounds, alkaline earth metal compounds and compounds of metals such as
titanium, tin, zinc, antimony, manganese, cobalt and germanium. The amount
of the catalyst is not specially limited, while it is preferably
approximately 0.0001 to 0.1% by weight based on the block copolymer to be
formed.
The time for the melt-reaction is not specially limited and differs
depending upon the polymer composition and polymerization temperature,
while it is approximately 30 minutes to 5 hours.
In the process of the present invention, the polyamide and at least one of
the aliphatic polyester and .epsilon.-caprolactone are melt-mixed/reacted
whereby the block copolymer can be obtained. As a final step, however, it
is required to substantially remove the above aromatic monohydroxy
compound from the polymerization system by distilling it off. The method
for removing the aromatic monohydroxy compound includes a method in which
the melting temperature is increased higher than the boiling point of the
aromatic monohydroxy compound under the polymerization conditions. A
method in which the pressure is reduced at the later-stage of the reaction
is effective for decreasing the boiling point of the aromatic monohydroxy
compound and distilling it off, and it can be preferably carried out. By
removing the aromatic monohydroxy compound, there can be obtained the
block copolymer composed substantially of the polyamide and the aliphatic
polyester.
For the atmosphere for the polymerization, it is preferred to use an
atmosphere of an inert gas such as nitrogen or argon under atmospheric
pressure or elevated pressure at an initial stage of the reaction, and
gradually decrease the pressure at a later stage of the reaction.
According to studies of the present inventors, it has been revealed that
some of block copolymers that can be produced by the process of the
present invention have the shape memory capability.
That is, according to the present invention, there is further provided a
polyamide/polycaprolactone block copolymer;
(A1) comprising a polyamide block composed substantially of at least one of
a recurring unit of the formula (1)-a.
##STR16##
and a recurring unit of the formula (2)-b,
##STR17##
wherein k is an integer of 4 to 12 and p is an integer of 4 to 12, and a
polycaprolactone block composed substantially of a recurring unit of the
formula (3)-a,
##STR18##
(B) satisfying the following expression (5),
T.sub.1 -T<100-C (5)
wherein T is the melting point (.degree.C.) of the above block copolymer,
T.sub.1 is the melting point (.degree.C.) of a polyamide composed of the
polyamide block and C is the content (wt. %) of the polyamide block,
(E) exhibiting the melting point derived from the polycaprolactone block in
the range of from about 40.degree. to 60.degree. C., and
(F) having shape memory and restoration capability.
The above block copolymer comprises a polyamide block composed
substantially of at least one of the recurring unit of the formula (1)-a
and the recurring unit of the above formula (2)-b and a polycaprolactone
block composed substantially of the recurring unit of the above formula
(3)-a.
The recurring unit of the formula (1)-a is a unit from the ring-opening of
.epsilon.-caprolactam.
In the formula (2)-b, k is an integer of 4 to 12, and p is an integer of 4
to 12. Examples of --(CH.sub.2).sub.k -- and --(CH.sub.2).sub.p -- include
tetramethylene, hexamethylene, octamethylene, decamethylene and
dodecamethylene.
As the polyamide to compose the polyamide block, nylon 6 and nylon 66 are
preferred.
The recurring unit of the above formula (3)-a is a unit from the
ring-opening of caprolactone.
In the above block copolymer, preferably, the content of the polyamide
block is 5 to 60% by weight, and the content of the polycaprolactone block
is 95 to 40% by weight.
When the above content of the polyamide block is less than 5% by weight or
larger than 60% by weight, the shape memory and restoration capability is
insufficient. The polyamide block/polycaprolactone block weight ratio is
preferably 7/93 to 50/50, more preferably 10/90 to 40/60.
In the above block copolymer, the length of each of the above polyamide
block and polycaprolactone block is not specially limited, while these
blocks preferably have chain lengths to such an extent that the melting
point derived from the polycaprolactone and the melting point of the
polyamide can be distinguishably observed when the block copolymer is
thermally analyzed by DSC.
In the above block copolymer having the shape memory capability, the
melting point (T) of the block copolymer and the melting point (T.sub.1)
of the polyamide block composing the block copolymer have the relationship
which satisfies the above expression (5), preferably the above expression
(5)-a.
The above block copolymer having the shape memory capability is required to
have a melting point, derived from the polycaprolactone block, in the
range of from approximately 40.degree. to 60.degree. C.
The above block copolymer has an intrinsic viscosity in the range of 0.5 to
5.0 when measured in a phenol/1,1,2,2-tetrachloroethane mixed solvent
(weight ratio 60/40) at 35.degree. C. When this intrinsic viscosity is
less than 0.5, undesirably, the block copolymer is insufficient in
mechanical properties and the shape memory and restoration capability.
When it is higher than 5.0, undesirably, the moldability is poor.
The block copolymer having the shape memory capability can be properly
produced by the already described method of the present invention.
A fiber having the dimension memory and restoration capability, i.e., a
shape memory fiber, can be obtained by melt-spinning the above block
copolymer having the shape memory capability.
The shape memory fiber of the present invention can be obtained by
melt-spinning the above block copolymer. The above shape memory fiber can
be produced by a known method in which a molten polymer is extruded
through a spinning nozzle by means of a plunger method or extrusion method
melt-extruder and the extrudate is cooled and solidified to form a fiber.
The temperature for melting the above polymer is preferably approximately
between T.sub.1 (melting point) of the polyamide component composing the
block copolymer and 320.degree. C., particularly preferably between about
(T.sub.1 of the polyamide component+10).degree.C. and about 300.degree. C.
The draft ratio for the spinning is preferably at least 5, particularly
preferably at least 10.
The dimension memory fiber of the present invention may be a monofilament
or a multifilament. The denier of the fiber is not specially limited,
while the denier of a single yarn is preferably approximately 1 to 200.
The dimension memory fiber of the present invention exhibits the shape
memory capability while it is in the state of an as-spun yarn, and it can
be used as it is. For obtaining the higher shape memory capability, it is
preferred to draw the as-spun yarn 1.5 to 6 times and subjecting the drawn
yarn to a relaxation treatment at a temperature equal to, or higher than,
60.degree. C. and lower than the T.sub.1 (melting point) of the polyamide
component. This treatment removes the strain which remains in the as-spun
yarn obtained by the melt-spinning, and improves the shape memory
capability.
The temperature for the above drawing is not specially limited, while it is
preferably approximately between 0.degree. and 100.degree. C., more
preferably 20.degree. and 80.degree. C. The draw ratio is preferably 1.5
to 6. When the draw ratio is less than 1.5, undesirably, it is difficult
to draw the fiber uniformly. When the draw ratio is greater than 6,
undesirably, the fiber is liable to break. The draw ratio is more
preferably 2 to 5.
Then, the drawn yarn is subjected to a relaxation treatment at a
temperature equal to, or higher than, 60.degree. C. and lower than the
T.sub.1 of the polyamide component. When the temperature for the
relaxation treatment is lower than 60.degree. C., it is not sufficient to
remove the strain of the as-spun yarn. When it is equal to, or higher
than, the T.sub.1 of the polyamide component, the polyamide undergoes
melting. The temperature for the relaxation treatment is preferably
between 60.degree. C. and (T.sub.1 of polyamide component -20).degree.C.,
particularly preferably between 60.degree. C. and (T.sub.1 of polyamide
component-40).degree.C.
The relaxation conditions are not specially limited, while the above drawn
yarn may be relaxed under limitation or relaxed under no tension. It is
preferably relaxed under no limitation and no tension. It may be drawn and
relaxed by a known method using the take-up rate difference of rollers.
The dimension memory fiber of the present invention is constituted of a
polyamide and polycaprolactone which are excellent in heat resistance and
moldability, and is remarkably excellent in melt-spinnability.
Using a polyamide crystal phase as a fixed phase and a polycaprolactone
crystal phase as a reversible phase, the shape memory fiber of the present
invention is excellent in shape memory and restoration capability, and
also excellent in durability in repeated use.
Due to the above properties, the shape memory fiber of the present
invention can be used as a fiber material, a fabric and component for
composite fibers. The above block copolymers of the present invention,
including the block copolymer having the shape memory capability, exhibit
excellent affinity to a thermoplastic resin which has no or poor
compatibility with a polyamide since they have a polyamide block and an
aliphatic polyester block.
According to the present invention, therefore, there is further provided an
intimate blend comprising a thermoplastic resin having no or poor
compatibility with a polyamide, a polyamide resin and the block copolymer
of the present invention as a compatibilizing agent, and there is also
provided an intimate blend comprising a thermoplastic resin having no or
poor compatibility with a polyamide and the block copolymer of the present
invention.
Typical examples of the above thermoplastic resin include a polyester
resin, a polycarbonate resin, a polyester carbonate resin, a
polystyrene-containing resin and a polyphenylene oxide resin.
The above polyester resin is obtained by the polycondensation of an
aromatic dicarboxylic acid and a diol.
Examples of the aromatic dicarboxylic acid include terephthalic acid,
isophthalic acid, naphthalene-2,6-dicarboxylic acid,
naphthalene-2,7-dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl
ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid and
5-carboxy-3-(4'-carboxyphenyl)-1,1,3-trimethlindane. These aromatic
dicarboxylic acids may be used alone or in combination. Particularly
preferred are terephthalic acid, isophthalic acid and
naphthalene-2,6-dicarboxylic acid.
Examples of the diol include glycol, hydroquinone, resorcinol,
dihydroxydiphenyl, bis(hydroxyphenyl)-alkane,
bis-(hydroxyphenyl)-cycloalkane, bis(hydroxyphenyl)-sulfide,
bis(hydroxyphenyl)-ether, bis-(hydroxyphenyl)-ketone,
bis-(hydroxyphenyl)-sulfone, bis-(hydroxyphenyl)-sulfoxide,
pentamethyl-(hydroxyphenyl)-indanol, .alpha.,
.alpha.'-bis-(hydroxyphenyl)-diisopropylbenzene, and compounds prepared by
alkylating or halogenating the benzene ring(s) of these compounds. Typical
examples which are most generally used are ethylene glycol, butylene
glycol and 2,2-bis(4-hydroxyphenyl)propane (to be abbreviated as
"bisphenol A" hereinafter). The above diols may be used in combination.
For obtaining a resin composition (blend) having desirable properties, it
is preferred to use a polyester having an intrinsic viscosity, measured in
a phenol/1,1,2,2-tetrachloroethane mixed solvent (weight ratio 60/40) at
35.degree. C., of at least 0.4.
The above polycarbonate resin is obtained from a diphenol or its derivative
and carbonic acid or its derivative.
Examples of the diphenol include hydroquinone, resorcinol,
dihydroxydiphenyl, bis(hydroxyphenyl)-alkane,
bis-(hydroxyphenyl)-cycloalkane, bis(hydroxyphenyl)-sulfide,
bis(hydroxyphenyl)-ether, bis-(hydroxyphenyl)-ketone,
bis-(hydroxyphenyl)-sulfone, bis-(hydroxyphenyl)-sulfoxide,
pentamethyl-(hydroxyphenyl)-indanol, .alpha.,
.alpha.'-bis-(hydroxyphenyl)-diisopropylbenzene, and compounds prepared by
alkylating or halogenating the benzene ring(s) of these compounds. The
most generally and typically used is "bisphenol A". The above diphenols
may be used in combination.
In addition to the carbonic acid or its derivative, a small amount of other
aromatic or aliphatic dicarboxylic acid or its derivative may be used as a
comonomer.
The derivatives of the diphenol and carbonic acid refer to esters, salts
and halides of these.
For obtaining a resin composition (blend) having desirable properties, it
is preferred to use a polycarbonate having a viscosity-average molecular
weight of 15,000 to 40,000.
Polystyrene-containing resin includes acrylonitrile styrene, acrylonitrile
butadiene styrene, etc.
Further, the above polyester carbonate resin, polystyrene-containing resin
and polyphenylene oxide resin do not have to be any special ones, and can
be selected from general resins known per se.
In the above intimate blend containing the block copolymer of the present
invention as a compatibilizing agent, the amount of the block copolymer of
the present invention per 100 parts by weight of the total of the above
thermoplastic resin and the polyamide resin is preferably 1 to 50 parts by
weight, more preferably 2 to 40 parts by weight, particularly preferably 3
to 30 parts by weight.
In the above case, the thermoplastic resin/polyamide resin weight ratio is
preferably 95/5 to 5/95, more preferably 90/10 to 10/90.
The polyamide resin as an object includes a variety of polyamide resins
obtained by the polycondensation of a three- or more-membered lactam,
.omega.-aminocarboxylic acid, dibasic acid and diamine.
Specifically, the polyamide resin includes polymers of
.epsilon.-caprolactam, aminocaproic acid, enatholactam, 7-aminoheptanoic
acid and 11-aminoundecanoic acid, and polymers or copolymers obtained by
the polycondensation of diamines such as butanediamine,
hexamethylenediamine, nonamethylenediamine, undecamethylenediamine and
m-xylylenediamine and dicarboxylic acids such as terephthalic acid,
isophthalic acid, adipic acid, sebacic acid, dodecanoic dibasic acid and
glutaric acid.
More specifically, the polyamide resin includes aliphatic polyamide resins
such as nylon 6, nylon 46, nylon 66, nylon 610, nylon 11, nylon 12, nylon
MXD6 and nylon 612, and aromatic polyamides such as
polytrimethylhexamethyleneterephthalamide and
polyhexamethyleneisophthalamide.
The polyamide resin used in the present invention preferably has an
intrinsic viscosity in the range of from 0.5 to 3.0, as an index for
molecular weight, when measured in m-cresol at 35.degree. C.
In the intimate blend containing the thermoplastic resin and the block
copolymer of the present invention, the amount of the block copolymer of
the present invention per 100 parts by weight of the thermoplastic resin
is preferably 1 to 200 parts by weight, more preferably 2 to 100 parts by
weight.
The above two intimate blends of the present invention may contain fibrous
reinforcing materials such as a glass fiber, a metal fiber, an aramid
fiber, a ceramic fiber, potassium titanate whisker, a carbonate fiber and
asbestos, and various fillers such as talc, calcium carbonate, mica, clay,
titanium oxide, aluminum oxide, glass flakes, a milled fiber, metal flakes
and a metal powder as required. Further, the two intimate blends of the
present invention may contain at least one of additives such as a heat
stabilizer, an oxidation stabilizer, a light stabilizer, a lubricant, a
pigment, a flame retarding agent and a plasticizer.
The method for producing the above intimate blends of the present invention
is not specially limited, while they can be easily produced by
melt-kneading the above various resins, the block copolymer of the present
invention and optionally the above various additives, etc.
EXAMPLES
The present invention will be detailed hereinafter with reference to
Examples, in which "part" stands for "part by weight".
The property values described in Examples were obtained by the following
methods.
(Intrinsic viscosity)
The intrinsic viscosity of a block copolymer and that of a polyester were
measured in a phenol/1,1,2,2-tetrachloroethane mixed solvent (weight ratio
60/40) at 35.degree. C.
The intrinsic viscosity of a polyamide as a raw material was measured in
m-cresol at 35.degree. C.
(Heat characteristics)
A polymer was measured for heat characteristics by DSC at a temperature
elevation rate of 10.degree. C./minute.
(COOH group)
The terminal COOH group of a polyamide as a raw material was titrated in a
benzyl alcohol solution using Phenol Red as an indicator and a 0.1N--NaOH
benzyl alcohol solution.
(NH.sub.2 group)
The terminal NH.sub.2 group was titrated in a m-cresol solution using a
Tymol Blue as an indicator and a 0.1N-p-toluenesulfonic acid aqueous
solution.
(Extraction amount)
Chips of a block copolymer were heat-refluxed in tetrahydrofuran whose
amount was 100 times as large as the weight of the block copolymer for 2
hours, then filtered and dried. The extraction amount (wt. %) of the block
copolymer in tetrahydrofuran was calculated on the basis of the weight of
the resultant insolubles.
Example 1
A reactor having a stirrer and a vacuum distillation system was charged
with 20 parts of particulate chips of nylon 6 having an intrinsic
viscosity of 1.41, a terminal COOH group amount of 66 mols/10.sup.6 g and
a terminal NH.sub.2 group amount of 15 mols/10.sup.6 g, 80 parts of
.epsilon.-caprolactone, 33 parts of p-chlorophenol and 0.06 part of
tetrabutyl titanate, and these components were heated up to 240.degree. C.
under atmospheric pressure in a nitrogen current. After about 10 minutes,
the nylon 6 chips were melted or dissolved to form a uniform solution.
This solution was allowed to react for 90 minutes under the same
conditions. During the reaction, the reaction solution showed a gradual
increase in viscosity to form a slightly turbid transparent liquid. The
reaction solution was temperature-increased up to 260.degree. C., and the
pressure was gradually decreased such that it was in a vacuum state of
about 20 mmHg after 10 minutes and further in a very high vacuum state of
1 mmHg or lower after 10 minutes therefrom. Then, the solution was allowed
to react for 30 minutes under the same conditions. During these
procedures, p-chlorophenol and unreacted .epsilon.-caprolactone were
distilled off from the polymerization system (distillation amount 41
parts).
The so-obtained polymer was a slightly turbid yellowish transparent polymer
in a molten state, and it had an intrinsic viscosity of 2.33 and showed
two melting peaks of 58.degree. C. and 207.degree. C. Further, the
extraction amount was 14%. FIG. 1 is the scanning electron microscopic
photograph of the polymer.
Comparative Example 1
The polymerization was carried out in the same manner as in Example 1
except that p-chlorophenol was not used. The resultant polymer was opaque
in a molten state, and it had an intrinsic viscosity of 1.86 and showed
two melting peaks of 59.degree. C. and 219.degree. C. When subjected to
the extraction treatment, the polymer was almost all dissolved and the
extraction solution was in a white suspension state. FIG. 2 is the
scanning electron microscopic photograph of the polymer.
Example 2
The polymer obtained in Example 1 or Comparative Example 1 was
melt-extruded through a nozzle having a diameter of 0.5 mm and a length of
1 mm with a Koka-type flow tester at 250.degree. C. The polymer obtained
in Example 1 showed excellent fluidity and melt-spinnability and gave a
transparent monofilament, while the polymer obtained in Comparative
Example 1 showed poor melt-spinnability and gave a white opaque
monofilament. These results show that the polyamide and the
polycaprolactone formed a block copolymer having very high uniformity in
structure in the production process of the present invention.
Example 3
A reactor having a stirrer and a vacuum distillation system was charged
with 20 parts of chips of nylon 6 having an intrinsic viscosity of 0.83, a
terminal COOH group amount of 140 mols/10.sup.6 g and a terminal NH.sub.2
group amount of 3 mols/10.sup.6 g, 80 parts of .epsilon.-caprolactone, 16
parts of phenol and 0.05 part of tetrabutyl titanate, and these components
were heated up to 250.degree. C. under atmospheric pressure in a nitrogen
current to react for 180 minutes. Then, the reaction mixture was
temperature-increased up to 260.degree. C., and gradually
pressure-decreased such that it was in a vacuum state at about 20 mmHg
after 10 minutes and further in a very high vacuum state of 1 mmHg or
lower after 10 minutes therefrom. Then, the reaction mixture was allowed
to react for 25 minutes under the same conditions. During this reaction
under vacuum, phenol and unreacted .epsilon.-caprolactone were distilled
off from the polymerization system (distillation amount 21 parts).
The so-obtained polymer was slightly yellowish in a molten state, and it
had an intrinsic viscosity of 2.18 and showed two melting peaks of
53.degree. C. and 201.degree. C. Further, the extraction amount was 11%.
Example 4
A reactor having a stirrer and a vacuum distillation system was charged
with 20 parts of nylon 66 having an intrinsic viscosity of 1.18, a
terminal COOH group amount of 83 mols/10.sup.6 g and a terminal NH.sub.2
group amount of 49 equivalents/10.sup.6 g, 80 parts of
.epsilon.-caprolactone, 33 parts of p-chlorophenol and 0.06 part of
tetrabutyl titanate, and these components were allowed to react at
260.degree. C. under atmospheric pressure in a nitrogen current for 90
minutes, at the same temperature under a weak vacuum of about 20 mmHg for
15 minutes and under a high vacuum of 1 mmHg or lower for 15 minutes.
During this reaction under vacuum, p-chlorophenol and unreacted
.epsilon.-caprolactone were distilled off (distillation amount 42 parts).
The so-obtained polymer was slightly turbid in a molten state, and it had
an intrinsic viscosity of 2.63 and showed two melting peaks of 46.degree.
C. and 233.degree. C. Further, the extraction amount was 10%.
Examples 5, 6 and 7
Predetermined amounts (shown in Table 1) of nylon 6 having an intrinsic
viscosity of 1.41, a terminal COOH group amount of 66 mols/10.sup.6 g and
a terminal NH.sub.2 group amount of 15 mols/10.sup.6 g and
.epsilon.-caprolactone, and 33 parts of p-chlorophenol and 0.06 part of
tetrabutyl titanate were polymerized in the same manner as in Example 1.
The so-obtained polymers were slightly turbid in a molten state. When
these polymers were melt-extruded in the same manner as in Example 2, they
were all excellent in melt-spinnability and gave transparent glossy
monofilaments. Table 1 shows the intrinsic viscosity, melting points and
tetrahydrofuran extraction amount of each of the polymers.
TABLE 1
______________________________________
Nylon .epsilon.-Capro- Melting
Extraction
6 lactone Intrinsic point amount
(part) (part) viscosity (.degree.C.)
(wt. %)
______________________________________
Ex. 5
40 60 1.83 53, 209
8.4
Ex. 6
60 40 1.59 46, 210
4.2
Ex. 7
80 20 1.22 213 1.3
______________________________________
Example 8
A reactor having a stirrer and a vacuum distillation system was charged
with 20 parts of particulate chips of nylon 6 having an intrinsic
viscosity of 0.85, a terminal COOH group amount of 140 mols/10.sup.6 g and
a terminal NH.sub.2 group amount of 8 mols/10.sup.6 g, 80 parts of
polycaprolactone (Placcel H-7, supplied by Daicel Chemical Industries,
Ltd.), 33 parts of p-chlorophenol and 0.06 part of tetrabutyl titanate,
and these components were heated up to 250.degree. C. under atmospheric
pressure in a nitrogen current. After about 10 minutes, the nylon 6 chips
were melted or dissolved to form a molten suspension. This suspension was
allowed to react for 90 minutes under the same conditions. During the
reaction, the reaction mixture showed a gradual decrease in viscosity to
form a slightly turbid transparent liquid. The reaction mixture was
temperature-increased up to 260.degree. C., and the pressure was gradually
decreased such that it was in a vacuum sate of about 20 mmHg after 10
minutes and further in a very high vacuum state of 1 mmHg or lower after
10 minutes therefrom. Then, the reaction mixture was allowed to react for
30 minutes under the same conditions. During these procedures,
p-chlorophenol was distilled off from the polymerization system
(distillation amount 41 parts).
The so-obtained polymer was a slightly turbid yellowish transparent polymer
in a molten state, and it had an intrinsic viscosity of 2.23 and showed
two melting peaks of 58.degree. C. and 206.degree. C. Its fusion
temperature was 152.degree. C. Further, the extraction amount in
tetrahydrofuran was 13%.
A piece of the above polymer was placed on a hot plate equipped with a
surface thermometer and a temperature adjuster, and the temperature of the
hot plate was gradually increased. A temperature at which the piece of the
polymer was melted and fused to the hot plate surface was taken as a
fusion temperature, which was used as an index for heat resistance.
Comparative Example 2
The polymerization was carried out in the same manner as in Example 8
except that p-chlorophenol was not used. The resultant polymer was opaque
in a molten state, and it had an intrinsic viscosity of 1.16 and showed
two melting peaks of 60.degree. C. and 218.degree. C. and a fusion
temperature of 57.degree. C. When subjected to the extraction treatment in
tetrahydrofuran, almost no insolubles remained, and the extraction
solution was in a white suspension state.
Example 9
The polymer obtained in Example 8 or Comparative Example 2 was
melt-extruded through a nozzle having a diameter of 0.5 mm and a length of
1 mm with a Koka-type flow tester at 210.degree. C. The polymer obtained
in Example 8 showed excellent fluidity and melt-spinnability and gave a
transparent monofilament, while the polymer obtained in Comparative
Example 2 showed poor melt-spinnability and gave a white opaque
monofilament. These results show that the polyamide and the aliphatic
polyester formed a block copolymer having very high uniformity in
structure in the production process of the present invention.
Example 10
A reactor having a stirrer and a vacuum distillation system was charged
with 50 parts of dimethyl sebacate, 200 parts of tetramethylene glycol and
0.06 parts of tetrabutyl titanate, and these components were heated up to
200.degree. C. under atmospheric pressure in nitrogen current to carry out
a general ester interchange reaction. After 2 hours, a stoichiometric
amount (about 64 parts) of methanol was found to be distilled off, and
then the reaction mixture was heated up to 250.degree. C. and heated at
this temperature for 2 hours. Then, the pressure was gradually decreased
such that it was in a vacuum state of about 20 mmHg after 10 minutes and
further in a very high vacuum state of 1 mmHg or lower after 10 minutes
therefrom. During these procedures, the reaction mixture showed a gradual
increase in viscosity. The reaction mixture was maintained under the same
conditions for 45 minutes to give an aliphatic polyester,
polytetramethylene sebacate, which was a slightly yellowish transparent
viscous material. This polyester has an intrinsic viscosity of 1.50.
Then, 50 parts of particulate chips of nylon, 6 having an intrinsic
viscosity of 1.41, a terminal COOH group amount of 8 mols/10.sup.6 g and a
terminal NH.sub.2 group amount of 14 mols/10.sup.6 g was added, and
melt-mixed with the above polyester. During these procedures, the reaction
melt gradually turned turbid in yellowish white. After the formation of a
mixture was found, 50 parts of p-chlorophenol was added, and the resultant
mixture was allowed to melt and react by heating it at 250.degree. C. for
60 minutes. During this reaction, the reaction melt altered from a turbid
state in whitish yellow to a brown transparent uniform melt. Then, the
pressure was gradually decreased such that it was in a vacuum state of
about 20 mmHg after 10 minutes and further in a very high vacuum state of
1 mmHg or lower after 30 minutes, and the melt was allowed to react for 30
minutes under the same conditions. During this reaction, p-chlorophenol
was distilled off from the polymerization system (distillation amount,
about 49 parts).
The so-obtained polymer was a slightly turbid yellowish transparent polymer
in a molten state, and it had an intrinsic viscosity of 1.06 and showed
two melting peaks of 62.degree. C. and 214.degree. C. and a fusion
temperature of 205.degree. C. Further, the extraction amount in
tetrahydrofuran was 5.6%.
Example 11
The polymerization was carried out in the same manner as in Example 10
except that tetramethylene glycol was replaced with neopentylene glycol.
The resultant polymer was was opaque in a molten state, and it had an
intrinsic viscosity of 2.07 and showed a melting peak of 209.degree. C.
and a fusion temperature of 170.degree. C. Further, the extraction amount
in tetrahydrofuran was 4.7%.
Comparative Examples 3 and 4
Examples 10 and 11 were repeated except that p-chlorophenol was not used.
The resultant polymers were opaque in a molten state. Table 2 shows the
intrinsic viscosity, melting point(s), fusion temperature and extraction
amount of each polymer.
TABLE 2
______________________________________
Melting Fusion Extraction
Intrinsic
point temperature
amount
viscosity
(.degree.C.)
(.degree.C.)
(wt. %)
______________________________________
Ex. 10 1.06 62, 214 205 5.6
Ex. 11 2.07 209 170 4.7
CEx. 3 1.71 68, 224 73 56
CEx. 4 1.45 216 25 53
______________________________________
Example 12
The reaction was carried out in the same manner as in Example 8 except that
p-chlorophenol was replaced with phenol. The resultant polymer was a
slightly turbid yellowish transparent polymer in a molten state, and it
had an intrinsic viscosity of 2.20 and showed two melting peaks of
57.degree. C. and 207.degree. C. and a fusion temperature of 150.degree.
C. Further, the extraction amount in tetrahydrofuran was 15%.
Example 13
The reaction was carried out in the same manner as in Example 8 except that
nylon 6 was replaced with particulate chips of nylon 66 having an
intrinsic viscosity of 1.18, a terminal COOH group amount of 83
mols/10.sup.6 g and a terminal NH.sub.2 group amount of 49 mols/10.sup.6
g, that the reaction initiation temperature was changed to 260.degree. C.
and that the reaction mixture after melted was temperature-increased to
270.degree. C.
The resultant polymer was a slightly turbid yellowish transparent polymer
in a molten state, and it had an intrinsic viscosity of 1.90 and showed
two melting peaks of 53.degree. C. and 230.degree. C. and a fusion
temperature of 210.degree. C. Further, the extraction amount in
tetrahydrofuran was 12 %.
Example 14
(Preparation of block copolymer)
A reactor having a stirrer and a vacuum distillation system was charged
with 20 parts of particulate chips of nylon 6 having an intrinsic
viscosity of 1.38, 80 parts of .epsilon.-caprolactone, 16 parts of phenol
and 0.05 part of tetrabutyl titanate, and these components were heated up
to 260.degree. C. under atmospheric pressure in a nitrogen current. After
about 10 minutes, the nylon 6 chips were melted or dissolved to form a
uniform solution. This solution was allowed to react for 60 minutes under
the same conditions. During the reaction, the reaction mixture showed a
gradual increase in viscosity to form a slightly turbid transparent melt.
Then, the pressure was gradually decreased and the melt was allowed to
react under a vacuum of about 20 mmHg for 15 minutes and further under a
very high vacuum of 1 mmHg or lower for 25 minutes. During this reaction
under reduced pressure, phenol was distilled off.
The so-obtained polymer had an intrinsic viscosity of 2.14, and showed two
melting peaks of 56.degree. C. and 203.degree. C. when measured by DSC.
Example 15
The block copolymer obtained in Example 14 was injection molded at a
polymer temperature of 240.degree. C., at a mold temperature of 20.degree.
C. and at a molding cycle of 70 seconds to prepare a plate-like test piece
having a size of 12 mm.times.3 mm.times.63 mm. During the injection
molding, the polymer showed excellent fluidity and moldability.
The above-prepared test piece was heated up to 80.degree. C. to soften it,
bent at its central portion at an angle of 180.degree. and cooled at room
temperature. By these procedures, the shape of the test piece in a bent
state was completely fixed.
Then, the above test piece was reheated up to 80.degree. C. to show a
restoration of 88% from a bending angle of 180.degree..
Examples 16-18
Predetermined amounts of particulate chips of nylon 6 having an intrinsic
viscosity of 1.38 and .epsilon.-caprolactone, and 18 parts, per 100 parts
of the total of the above polymer components, of phenol and 0.05 part, per
100 parts of the same, of tetrabutyl titanate were polymerized in the same
manner as in Example 14, to prepare block copolymers composed of nylon 6
and polycaprolactone.
The so-obtained polymers were injection molded, and evaluated for shape
memory and restoration capability, in the same manner as in Example 15.
Table 3 shows the results. It is seen that the resin of the present
invention is excellent in shape memory and restoration capability.
TABLE 3
______________________________________
Melting
Shape
.epsilon.-Capro- ing restoration
Nylon 6 lactone Intrinsic point capability
(part) (part) viscosity (.degree.C.)
(%)
______________________________________
Ex. 16 15 85 2.80 56, 199
90
Ex. 17 30 70 2.35 55, 207
88
Ex. 18 40 60 1.87 53, 209
85
______________________________________
Example 19
A reactor having a stirrer and a vacuum distillation system was charged
with 20 parts of chips of nylon 66 having an intrinsic viscosity of 1.18,
80 parts of .epsilon.-caprolactone, 25 parts of p-chlorophenol and 0.05
part of tetrabutyl titanate, and these components were allowed to react at
260.degree. C. for 75 minutes in a nitrogen current under atmospheric
pressure, under a weak vacuum of about 20 mmHg for 15 minutes and further
under a very high vacuum of 1 mmHg or lower for 29 minutes. The
so-obtained polymer had an intrinsic viscosity of 2.24, and showed two
melting peaks of 49.degree. C. and 235.degree. C.
Example 20
The block copolymer obtained in Example 19 was injection molded at a
polymer temperature of 250.degree. C., at a mold temperature of 20.degree.
C. and at a molding cycle of about 75 seconds to prepare a plate-like test
piece similar to that prepared in Example 15. This test piece was
evaluated for shape memory and restoration capability in the same manner
as in Example 15 to show a restoration of 90% from a bending angle of
180.degree..
Example 21
The polymer obtained in Example 14 was crashed, and then melt-spun through
a nozzle having a diameter of 0.3 mm and a length of 0.7 mm by means of an
apparatus equipped with a monohole spinning orifice at a polymer
temperature of 210.degree. C. In this case, the polymer showed excellent
melt-spinnability. There was obtained a slightly brownish monofilament
yarn having a size of 29 denier. Then, this yarn was drawn about 4 times
at 30.degree. C. by means of a drawing apparatus.
The above-obtained block copolymer drawn yarn was subjected to a relation
treatment under no tension by maintaining it in an oven at 80.degree. C.
for 5 minutes.
(Evaluation for dimension memory capability)
The length of the yarn obtained by the above treatment was taken as 100,
and the yarn was stretched up to a length of 150%. At this time, it was
confirmed that the yarn (fiber) did not restore its original length (that
the length was fixed at room temperature), and then the yarn was heat
treated in oven at 80.degree. C. for 5 minutes. The yarn was allowed to
cool to room temperature, and then measured for a length for evaluating
the shape restoration capability.
The heat-treated yarn nearly restored its original length. Further, the
yarn was evaluated for restoration capability as the stretch ratio was
increased. FIG. 3 shows the results. In FIG. 3, each void column indicates
a length (%) up to which the yarn was stretched before heat treatment, and
each slanting-lined column indicates a length (%) to which the yarn
restored its length after heat treatment.
Example 22
The reaction was carried out in the same manner as in Example 21 except
that nylon 6 as a polyamide was replaced with particulate chips of nylon
66 having an intrinsic viscosity of 1.18 and the heating temperature was
changed to 270.degree. C. The so-obtained polymer had an intrinsic
viscosity of 2.24 and showed two crystal melting points at 44.degree. C.
and 234.degree. C. when measured by DSC. A filament was produced from the
above polymer in the same manner as in Example 21 and evaluated. FIG. 4
shows the results. Void columns and slanting-lined columns indicate the
same meanings as in FIG. 3.
These results show that the fiber of the present invention has the
excellent dimension restoration capability.
Examples 23-26 and Comparative Example 5
Each of the block copolymers obtained in Examples 1, 4, 5 and 8 was
respectively melt-extruded through a slit having a width of 10 mm and a
thickness of 1 mm at a polymer temperature of 230.degree. to 250.degree.
C. to form tape-shaped samples having a width of about 7 mm and a
thickness of about 0.5 mm. Each sample was cut to a length of 100 mm and
burled about 20 cm deep in soil covered with lawn. After 180 days, the
buried samples were taken out and measured for weights.
In Comparative Example 5, a polycaprolactone (Placcel H7, supplied by
Daicel Chemical Industries, Ltd.) was molded in the same manner as above,
and tested in the same manner as above.
Table 4 shows the results.
These results show that the block copolymer of the present invention
exhibits biodegradability equivalent to, or higher than, that of
polycaprolactone and has heat resistance which permits the use thereof at
a temperature equal to, higher than, the melting point of
polycaprolactone.
TABLE 4
______________________________________
Block Polymer Melting Weight retention
copolymer composition point after 180
from: (wt. %) (.degree.C.)
days (wt. %)
______________________________________
Ex. 23 Ex. 1 nylon 6 (20)
58, 207
63
polycapro-
lactone 0)
Ex. 24 Ex. 4 nylon 66 (20)
46, 233
75
polycapro-
lactone (80)
Ex. 25 Ex. 5 nylon 6 (40)
53, 209
70
polycapro-
lactone (60)
Ex. 26 Ex. 8 nylon 6 (20)
58, 206
60
polycapro-
lactone (80)
CEx. 5 -- polycapro- 60 86
lactone
______________________________________
Examples 27-30 and Comparative Examples 6 and 7
Each of the polymers obtained in Examples 1, 4, 5 and 8 was respectively
melt-extruded through a nozzle having a diameter of 0.3 mm and a length of
0.7 mm at a polymer temperature of 220.degree. to 250.degree. C., to
prepare monofilaments. The monofilaments were drawn at 30.degree. C. up to
a predetermined draw ratio to obtain drawn yarns. Table 5 shows the
mechanical properties of these yarns and amounts of soluble total organic
carbon (TOC) hydrolyzed by enzyme.
In the test for the hydrolysis by enzyme, 10 ml of a 0.2M phosphoric acid
buffer solution and 4 mg of lipase (trade name: Lipase, Lyophilized,
Rhizopus delemer, Fine Grade, supplied by Seikagaku Corporation) as a
degradation enzyme were added to 1 g of the fiber, and water was added
such that the total amount became 20 ml. The mixture was allowed to react
at 37.degree. C. for 24 hours and measured for a total amount of
solubilized organic carbon (TOC). The TOC in this case refers to a value
obtained by deducting TOC of a sample containing no degradation enzyme and
TOC obtained when the degradation enzyme alone was used. Table 5 shows the
results.
Table 5 also shows the results of fibers from a polycaprolactone (Placcel
H7, supplied by Daicel Chemical Industries, Ltd.) and nylon 6 (Intrinsic
viscosity 1.21) for comparison (Comparative Examples 6 and 7).
It is seen that the drawn yarn formed from the block copolymer of the
present invention has excellent mechanical properties and hydrolyzability
by enzyme.
TABLE 5
______________________________________
Block Tensile Elonga-
copolymer Draw strength tion TOC
from: ratio (g/de) (%) (mg/l)
______________________________________
Ex. 27 Ex. 1 5.5 3.6 46 940
Ex. 28 Ex. 4 6.0 4.2 45 870
Ex. 29 Ex. 5 5.0 3.8 40 730
Ex. 30 Ex. 8 5.0 3.2 38 910
CEx. 6 (polycapro-
6.0 1.7 31 1,300
lactone)
CEx. 7 (nylon 6)* 4.5 5.4 20 320
______________________________________
*: Draw temperature = 80.degree. C.
Example 31
A reactor having a stirrer and a vacuum distillation system was charged
with 50 parts of particulate chips of nylon 6 having an intrinsic
viscosity of 1.41, 50 parts of .epsilon.-caprolactone, 25 parts of phenol
and 0.06 part of tetrabutyl titanate, and these components were heated up
to 220.degree. C. under atmospheric pressure in a nitrogen current. After
about 10 minutes, the nylon 6 chips were melted or dissolved to form a
uniform solution. This solution was allowed to react for 90 minutes under
the same conditions. During the reaction, the reaction mixture showed a
gradual increase in viscosity to become a slightly turbid transparent
liquid. Then, the temperature was increased to 260.degree. C., and the
pressure was gradually decreased such that it was under a vacuum of about
20 mmHg after 10 minutes and further in a high vacuum state at 1 mmHg or
lower after 10 minutes therefrom. Then, the liquid was allowed to react
under the same conditions for 30 minutes. During this reaction, phenol and
unreacted .epsilon.-caprolactone were distilled off from the
polymerization system.
The so-obtained polymer was a slightly turbid yellowish transparent
polymer, and it had an intrinsic viscosity of 2.16 and showed two melting
peaks at 56.degree. C. and 209.degree. C. The extraction amount in
tetrahydrofuran was 3.8%.
Example 32
A reactor having a stirrer and a vacuum distillation system was charged
with 40 parts of particulate chips of nylon 6 having an intrinsic
viscosity of 0.85, 60 parts of polycaprolactone (Placcel H7, supplied by
Daicel Chemical Industries, Ltd.), 33 parts of p-chlorophenol and 0.06
part of tetrabutyl titanate, and these components were heated up to
250.degree. C. under atmospheric pressure in a nitrogen current. After
about 10 minutes, the nylon 6 chips were melted or dissolved to form a
uniform solution. This solution was allowed to react for 90 minutes under
the same conditions to become a slightly turbid transparent liquid. Then,
the temperature was increased to 260.degree. C., and the pressure was
gradually decreased such that it was under a vacuum of about 20 mmHg after
10 minutes and further in a high vacuum state at 1 mmHg or lower after 30
minutes therefrom. Then, the liquid was allowed to react under the same
conditions for 30 minutes. During this reaction, p-chlorophenol was
distilled off from the polymerization system.
The so-obtained polymer was a slightly turbid yellowish transparent polymer
in a molten state, and it had an intrinsic viscosity of 1.84 and showed
two melting peaks at 57.degree. C. and 207.degree. C. The extraction
amount in tetrahydrofuran was 5.6%.
Examples 33-37 and Comparative Example 8
Predetermined amounts of a polycarbonate resin (Trade name: Panlite L1250,
supplied by Teijin Chemicals Ltd), a nylon 6 resin having an intrinsic
viscosity of 1.4 and the block copolymer obtained in Examples 31 or 32
were dried by a conventional method, and then melt-blended with a twin
screw extruder having 30 mm.phi. unidirectionally revolving screws at a
polymer temperature of 280.degree. C. for an average residence time of
about 3 minutes.
The above-obtained composition was injection molded by means of an
injection molding machine (M-50B, supplied by Meiki Seisakusho) at a
polymer temperature of 280.degree. C. at a mold temperature of 80.degree.
C. at a molding cycle of 90 seconds to prepare test pieces. Table 6 shows
the properties of the test pieces. For comparison, Table 6 also shows the
results of a composition containing no block copolymer. These results show
that the resin composition of the present invention is excellent in
mechanical properties, in particular, remarkably improved in impact
resistance.
Since a polycarbonate resin and a polyamide resin had no compatibility with
each other, a molded article obtained in Comparative Example 8 had a
surface having pearl-like patterns, while molded articles obtained from
the compositions of the present invention were free of a speckled surface
and each composition was in a microdispersion state since the above two
components were improved in compatibility.
TABLE 6
__________________________________________________________________________
unit Ex. 33
Ex. 34
Ex. 35
Ex. 36
Ex. 37
CEx. 8
__________________________________________________________________________
COMPOSITION
Polycarbonate
(part)
45 50 40 45 60 50
Polyamide (part)
45 40 40 45 30 50
Block copolymer
(part)
Ex. 31
Ex. 31
Ex. 31
Ex. 32
Ex. 32
--
10 10 20 10 10
PROPERTIES OF
MOLDED ARTICLE
Tensile (kg/cm.sup.2)
560 590 570 590 620 380
strength
Flexural (kg/cm.sup.2)
730 690 630 750 770 660
strength
Flexural (kg/cm.sup.2)
16,800
17,200
14,000
17,000
18,200
20,600
modulus
Impact strength
(kg .multidot. cm/cm)
7.4 9.1 14.2 7.8 11.6 3.6
Izod, notched
Water absorption
(%) 1.0 0.9 1.1 1.0 0.7 1.1
percentage
(23.degree. C., 24 hr)
Solvent (%) 1.5 1.8 2.3 1.6 2.8 2.0
resistance*
__________________________________________________________________________
*: Weight increase ratio when a sample was immersed in xylene at
23.degree. C. for 24 hours.
Examples 38-40 and Comparative Examples 9 and 10
Predetermined amounts of either a polybutylene terephthalate resin
(intrinsic viscosity 0.88, supplied by Teijin Ltd.) or a polyarylate
(U-100, supplied by Unitika, Ltd.), a nylon 6 resin having an intrinsic
viscosity of 1.4 and the block copolymer obtained in Examples 31 or 32
were dried by a conventional method, and then melt-blended with a twin
screw extruder having 30 mm.phi. unidirectionally revolving screws at a
polymer temperature of 280.degree. C. for an average residence time of
about 3 minutes.
The above-obtained composition was injection molded by means of an
injection molding machine (M-50B, supplied by Meiki Seisakusho) at a
polymer temperature of 280.degree. C. at a mold temperature of 80.degree.
C. at a molding cycle of 90 seconds to prepare test pieces. Table 7 shows
the properties of the test pieces. For comparison, Table 7 also shows the
results of compositions containing no multi-block copolymer. These results
show that the resin composition of the present invention is excellent in
mechanical properties, in particular, remarkably improved in impact
resistance.
Further, since a polyester resin and a polyamide resin have no
compatibility with each other, a molded article obtained in Comparative
Example 9 had a surface having pearl patterns, while molded articles
obtained from the compositions of the present invention were free of a
speckled surface and each composition was in a microdispersion state since
the above two components were improved in compatibility.
TABLE 7
__________________________________________________________________________
unit Ex. 38
Ex. 39
Ex. 40
CEx. 9
CEx. 10
__________________________________________________________________________
COMPOSITION
Polybutylene
(part)
45 50 -- 50 --
terephthalate
Polyarylate
(oart)
-- -- 25 -- 30
Polyamide (part)
45 40 65 50 70
Block copolymer
(part)
Ex. 31
Ex. 32
Ex. 32
-- --
10 10 10
PROPERTIES OF
MOLDED ARTICLE
Tensile (kg/cm.sup.2)
522 511 1,120
516 806
strength
Elongation
(%) 191 196 98 180 51
Flexural (kg/cm.sup.2)
754 740 860 733 854
strength
Flexural (kg/cm.sup.2)
18,700
17,500
19,100
18,500
18,100
modulus
Impact strength
(kg .multidot. cm/cm)
8.1 7.5 10.5 4.5 5.2
Izod, notched
__________________________________________________________________________
Examples 41-44 and Comparative Examples 11 and 12
Each of the block copolymers obtained in Examples 1, 5, 6 and 7 were
injection molded at a polymer temperature of 230.degree. C. at a mold
temperature 30.degree. C. Table 8 shows the properties of the so-obtained
articles.
For comparison, Table 8 also shows the properties of molded articles from
nylon 6 (intrinsic viscosity 1.41) and a polycaprolactone (Placcel H-4,
supplied by Dalcel Chemical Industries, Ltd.). It is seen that the block
copolymer of the present invention has remarkably high impact resistance.
TABLE 8
__________________________________________________________________________
Ex. 41
Ex. 42
Ex. 43
Ex. 44
CEx. 11
CEx. 12
__________________________________________________________________________
Block copolymer
Ex. 1
Ex. 5
Ex. 6
Ex. 7
-- --
from:
POLYMER COMPOSITION
Nylon 6 (20)
(40)
(60)
(80)
(100)
(0)
Polycaprolactone
(80)
(60)
(40)
(20)
(0) (100)
(wt. %)
PROPERTIES OF
MOLDED ARTICLE
Tensile strength
220 290 490 560 1,400
210
(kg/cm.sup.2)
Elongation >500
350 380 240 130 >500
at break (%)
Flexural strength
120 140 140 310 880 210
(kg/cm.sup.2)
Flexural modulus
2,900
3,500
3,500
7,700
21,000
5,100
(kg/cm.sup.2)
Impact strength
NB NB NB NB 3.8 4.5
1/8", notched
(kg .multidot. cm/cm)
Surface hardness
55 58 63 71 85 64
(Shore D)
__________________________________________________________________________
NB: not break
Example 45 and Comparative Example 13
70 Parts of a polycarbonate (trade name: Panlite L1250, supplied by Teijin
Chemicals Ltd) and 30 parts of the block copolymer obtained in Example 7
were dry-blended, and the blend was injection molded at a polymer
temperature of 280.degree. C. at a mold temperature of 80.degree. C. Table
9 shows the properties of the so-obtained molded article. For comparison,
Table 9 also shows the properties of a molded article from a blend
containing nylon 6 (intrinsic viscosity 1.21) in place of the block
copolymer.
TABLE 9
______________________________________
Comparative
Example 45
Example 13
______________________________________
POLYMER COMPOSITION
(wt. %)
Polycarbonate 70 70
Block copolymer 30 --
Nylon 6 -- 30
Tensile strength 500 440
(kg/cm.sup.2)
Elongation 140 30
at break (%)
Flexural strength 720 780
(kg/cm.sup.2)
Flexural modulus 19,000 22,300
(kg/cm.sup.2)
Impact strength 12.5 4.2
1/8", notched
(kg .multidot. cm/cm)
Heat deformation 118 119
temperature (.degree.C.)
______________________________________
Examples 46 and 47 and Comparative Examples 14 and 15
40 Parts of either ABS resin (UT.sub.61, supplied by Mitsui Toatsu
Chemicals, Inc.) or AS resin (AS-230, supplied by Japan Synthetic Rubber
Co., Ltd.), 40 parts of nylon 6 (intrinsic viscosity 1.21) and 20 parts of
the block copolymer obtained in Example 31 were dry-blended, and the blend
was injection molded at a polymer temperature of 230.degree. C. at a mold
temperature of 30.degree. C. Further, the injection molding was carried
out in the same manner as above except that the block copolymer was not
used. Table 10 shows the properties of the so-obtained molded articles.
These results show that the block copolymer of the present invention is
effective as a compatibilizing agent.
TABLE 10
______________________________________
Ex. 46 Ex. 47 CEx. 14 CEx. 15
______________________________________
POLYMER
COMPOSITION
(wt. %)
ABS resin 40 -- 40 --
AS resin -- 40 -- 40
Nylon 6 40 40 40 40
Block copolymer
20 20 -- --
Tensile strength
480 530 510 560
(kg/cm.sup.2)
Elongation 270 320 20 5
at break (%)
Flexural strength
720 860 850 900
(kg/cm.sup.2)
Flexural modulus
19,000 24,000 21,400 29,000
(kg/cm.sup.2)
Impact strength
9.5 7.1 5.6 2.3
1/8", notched
(kg .multidot. cm/cm)
______________________________________
Example 48
50 Parts of AS resin (AS-230, supplied by Japan Synthetic Rubber Co., Ltd.)
and 50 parts of the block copolymer obtained in Example 7 were
dry-blended, and the blend was injection molded at a polymer temperature
of 225.degree. C. at a mold temperature of 30.degree. C. The resultant
molded article showed a tensile strength of 580 kg/cm.sup.2, an elongation
of 180% at break, a flexural strength of 890 kg/cm.sup.2, a flexural
modulus of 25,800 kg/cm.sup.2 and an impact strength of 6.8 kg.cm/cm.
Example 49
The polymerization was carried out in the same manner as in Example 31
except that 5 parts of sodium dimethyl 5-sulfoisophthalate and 2 parts of
3-methyl-1,5-pentanediol were added and that the reaction time at
220.degree. C. was changed to 180 minutes. The so-obtained polymer was
yellowish transparent, and had an intrinsic viscosity of 1.62 and a
melting point of 188.degree. C.
The above polymer was injection molded in the same manner as in Example 41
to prepare a disk-shaped molded article having a diameter of 50 mm and a
thickness of 2 mm. The molded article was allowed to stand at 20.degree.
C. at a relative humidity of 65%, and then measured for a surface
resistivity at a voltage of 1,000 V with an ultra-insulation measuring
meter (SM-8210 supplied by Towa Denpa Kogyo K. K.) according to JIS K6911
to show 1.8.times.10.sup.10 .OMEGA..
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